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1.
The β‐Agostic Structure in (C5Me5)2Sc(CH2CH3): Solid‐State NMR Studies of (C5Me5)2Sc−R (R=Me,Ph, Et)
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Damien B. Culver Winn Huynh Dr. Hosein Tafazolian Dr. Ta‐Chung Ong Prof. Dr. Matthew P. Conley 《Angewandte Chemie (International ed. in English)》2018,57(30):9520-9523
Multinuclear solid‐state NMR studies of Cp*2Sc?R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc?Et complex contains a β‐CH agostic interaction. The static central transition 45Sc NMR spectra show that the quadrupolar coupling constants (Cq) follow the trend of Ph≈Me>Et, indicating that the Sc?R bond is different in Cp*2Sc?Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by Cβ in Sc?CH2CH3 is related to coupling between the filled σC‐C orbital and the vacant orbital. 相似文献
2.
del Mar Conejo M Fernández R del Río D Carmona E Monge A Ruiz C Márquez AM Sanz JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4452-4461
The beryllocenes [Be(C(5)Me(4)H)(2)] (1), [Be(C(5)Me(5))(2)] (2), and [Be(C(5)Me(5))(C(5)Me(4)H)] (3) have been prepared from BeCl(2) and the appropriate KCp' reagent in toluene/diethyl ether solvent mixtures. The synthesis of 1 is facile (20 degrees C, overnight), but generation of decamethylberyllocene 2 demands high temperatures (ca. 115 degrees C) and extended reaction times (3-4 days). The mixed-ring beryllocene 3 is obtained when the known [(eta(5)-C(5)Me(5))BeCl] is allowed to react with K[C(5)Me(4)H], once more under somewhat forcing conditions (115 degrees C, 36 h). The structures of the three metallocenes have been determined by low-temperature X-ray studies. Both 1 and 3 present eta5/eta1 geometries of the slip-sandwich type, whereas 2 exhibits an almost regular, ferrocene-like, sandwich structure. In the mixed-ring compound 3, C(5)Me(5) is centrally bound to beryllium and the eta(1)-C(5)Me(4)H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the eta(1)-ring of 1. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds 2 and 3, and a comparison with the bonding in [Be(C(5)H(5))(2)] has been made. As for the latter molecule, energy differences between the eta5/eta5 and the eta5/eta1 structures of 2 are very small, being of the order of a few kcal mol(-1). Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C(5)Me(5))(2)] than for [Be(C(5)H(5))(2)] due to larger charge delocalization and to increased polarizability of the C(5)Me(5) fragment. 相似文献
3.
D. P. Krut’ko M. V. Borzov Long Yu Liao Wan Li Nie A. V. Churakov J. A. K. Howard D. A. Lemenovskii 《Russian Chemical Bulletin》2006,55(9):1574-1580
The new side-chain functionalized cyclopentadienyl ligand LiC5H4CPh2CH2R (R is 1-methylimidazol-2-yl) as lithium salt 2, the trimethylsilyl derivative Me3SiC5H4CPh2CH2R (3), and the ligand in the CH form (4) were prepared starting from 6,6-diphenylfulvene and 1,2-dimethylimidazole lithiated at the 2-Me group (1) and then characterized. The half-sandwich complexes (η5:η 1-C5H4CPh2CH2R)TiCl3 (5) and (η5:η 1-C5H4CPh2CH2R)ZrCl3 (6) were synthesized. The molecular structure of complex 5 was established by X-ray diffraction. Complexes 5 and 6 exhibit dynamic behavior in solution associated with degenerate interconversion of the pseudo-six-membered metallacycle.
For titanium complex 5 in a solvating solvent, a dynamic process due to intramolecular dissociation—coordination of the imidazole fragment was observed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1518–1524, September, 2006. 相似文献
4.
Three heterometallic Au-Pt complexes [Pt2(PPh3)4(mu-S)(mu 3-S)Au(PPh3)][PF6] (2), [Pt2(PPh3)4(mu 3-S)2Au2(mu-dppm)]-[PF6]2 (3), and [Pt2(PPh3)4(mu 3-S)2Au2(mu-dppf)][PF6]2 (4) have been synthesized from Pt2(PPh3)4(mu-S)2 (1) [dppm = Ph2PCH2PPh2; dppf = (C5H4PPh2)2Fe] and characterized by single-crystal X-ray crystallography. In 2, the Au(I) atom is anchored on only one of the sulfur centers. In 3 and 4, both sulfur atoms are aurated, showing the ability of 1 to support an overhead bridge structure, viz. [Au2(P-P)], with or without the presence of Au-Au bond. The change of dppf to dppm facilitates such active interactions. Two stereoisomers of complex 3 (3a,b) have been obtained and characterized by single-crystal X-ray crystallography. NLDFT calculations on 2 show that the linear coordination mode is stabilized with respect to the trigonal planar mode by 14.0 kJ/mol. All complexes (2-4) are fluxional in solution with different mechanisms. In 2, the [Au(PPh3)] fragment switches rapidly between the two sulfur sites. Our hybrid MM-NLDFT calculations found a transition state in which the Au(I) bears an irregular trigonal planar geometry (delta G++ = 19.9 kJ/mol), as well as an intermediate in which Au(I) adopts a regular trigonal planar geometry. Complexes 3a,b are roughly diastereoisomeric and related by sigma (mirror plane) conversion. This symmetry operation can be broken down to two mutually dependent fluxional processes: (i) rapid flipping of the dppm methylene group across the molecular plane defined by the overhead bridge; (ii) rocking motion of the two Au atoms across the S...S axis of the (Pt2S2) core. Modeling of the former by molecular mechanics yields a steric barrier of 29.0 kJ/mol, close to that obtained from variable-temperature 31P(1Hz) NMR study (33.7 kJ/mol). In 4, the twisting of the ferrocenyl moiety across the S...S axis is in concert with a rocking motion of the two gold atoms. The movement of dppf is sterically most demanding, and hence, 4 is the only complex that shows a static structure at lower temperatures. Pertinent crystallographic data: (2) space group P1, a = 15.0340(5) A, b = 15.5009(5) A, c = 21.9604(7) A, alpha = 74.805(1) degrees, beta = 85.733(1) degrees, gamma = 78.553(1) degrees, R = 0.0500; (3a) space group Pna2(1), a = 32.0538(4) A, b = 16.0822(3) A, c = 18.9388(3) A, R = 0.0347; (3b) space group Pna2(1), a = 31.950(2) A, b = 16.0157(8) A, c = 18.8460(9) A, R = 0.0478; (4) space group P2(1)/c, a = 13.8668(2) A, b = 51.7754(4) A, c = 15.9660(2) A, beta = 113.786(1) degrees, R = 0.0649. 相似文献
5.
Oligophosphanide Anions: Syntheses and Molecular Structures of [K2(PMDETA)2(P4Ph4)], [K2(PMDETA)(P4tBu4)]2 and [K(PMDETA)(THF){cyclo‐(P5tBu4)}] (PMDETA = NMe(CH2CH2NMe2)2) The alkali metal tetraphosphanediides [K2(PMDETA)2(P4Ph4)] ( 1 ) and [K2(PMDETA)(P4tBu4)]2 ( 2 ) [PMDETA = NMe(CH2CH2NMe2)2] were synthesized via reaction of PhPCl2 or tBuPCl2 with 2.5 equiv. potassium and characterized by X‐ray crystallography and 31P NMR spectroscopy. As in other ion contact complexes of the type M2(P4R4) (M = alkali metal) the solid‐state structures are retained in solution. While 1 could be prepared in comparatively good yield (54 %), 2 was only isolated in very modest yield and with low purity as [K(PMDETA)(THF){cyclo‐(P5tBu4)}] ( 3 ) was formed as a side product in this case. 3 was also characterized by X‐ray crystallography and 31P NMR spectroscopy. 相似文献
6.
Ehab M. Al‐Shami Adnan S. Abu‐Surrah Martti Klinga Hamdallah A. Hodali 《无机化学与普通化学杂志》2002,628(6):1433-1436
The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by 1H NMR and 13C NMR. Reactions of S‐P3 with [PdCl2(PhCN)2] afforded the complexes [PdCl2(S‐P3)] ( I ) and [PdCl2(S‐P3)2] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P21/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)Å3, Z = 4. Likewise, compound II crystallizes in monoclinic space group P21/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)Å3, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom. 相似文献
7.
鉴于含硅-过渡金属键化合物作为催化剂具有重要的应用价值, 在我们最近发现的化合物(η5,η5-C5H4Me2SiSi-Me2C5H4)Fe2(CO)4 (1)的硅硅键和铁铁键复分解重排反应可以有效地合成含有两个硅铁键的环状化合物[Me2Si-η5-C5H4- Fe(CO)2]2 (2)的基础上, 对该硅铁键环状化合物的三苯基膦取代衍生物[Me2Si-η5-C5H4-Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe(CO)2-n(PPh3)n] (3: n=0, 5: n=1)的合成方法进行了研究. 发现化合物1在三苯基膦存在下的复分解重排反应是合成单三苯基膦取代产物3的最好方法; 而双三苯基膦取代化合物5则可通过光照条件下2与三苯基膦发生羰基取代反应而得到, 产物中含有的顺反异构体可利用制备薄层色谱法分离. 利用X射线衍射法测定了化合物3的分子结构, 考察了三苯基膦配体的存在对分子结构的影响以及三苯基膦与铁形成的配位键的稳定性. 相似文献
8.
Piyush Deokar Dr. Monica Vasiliu Prof. Dr. David A. Dixon Prof. Dr. Karl O. Christe Prof. Dr. Ralf Haiges 《Angewandte Chemie (International ed. in English)》2016,55(46):14350-14354
The binary zirconium and hafnium polyazides [PPh4]2[M(N3)6] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF4 by fluoride–azide exchange reactions with Me3SiN3 in the presence of two equivalents of [PPh4][N3]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N3)4], [M(N3)5]? and [M(N3)6]2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels. 相似文献
9.
Siti Syaida Sirat Imthyaz Ahmed Khan Omar Bin Shawkataly Mohd Mustaqim Rosli 《无机化学与普通化学杂志》2014,640(10):2019-2024
The reaction of Ru3(CO)10(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh3, P(C6H4Cl‐p)3 and PPh2(C6H4Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru3(CO)9(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, 1H NMR, 13C{1H} NMR and 31P{1H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths. 相似文献
10.
Reactions of [{M(μ‐Cl)(coe)2}2] (M = Rh, Ir; coe = cis‐cyclooctene) with the secondary phosphane tBu2PH under various molar ratios were investigated. Probably, for kinetic reasons, the reaction behavior of the rhodium species differed from that of the iridium analogue in some instances. During these studies complexes [MCl(tBu2PH)3] [M = Rh ( 1 ), Ir ( 2 )] were isolated, and solution variable‐temperature 31P{1H} NMR studies revealed that these complexes show a conformational rigidity on the NMR time scale. Spectra recorded in the temperature range from 173 to 373 K indicated in each case only one rotamer containing three chemically nonequivalent phosphanes due to the restricted rotation of these ligands about the M–P bonds and the tert‐butyl substituents around the P–C(tBu) bonds, respectively. Compound 1 showed in solution already at room temperature in several solvents a dissociation of a phosphane ligand affording the known complex [{Rh(μ‐Cl)(tBu2PH)2}2] beside the free phosphane. In contrast to these findings, the iridium analogue 2 remained completely unchanged under similar conditions and exhibited, therefore, some kinetic inertness. For a better understanding of the NMR spectroscopic investigations, the molecular structure of 1 in the solid state was confirmed by X‐ray crystallography. 相似文献
11.
Elise Duhamel Alpar Pöllnitz Adina Stegarescu Prof. Dr. Anca Silvestru 《无机化学与普通化学杂志》2011,637(10):1355-1360
Redistribution reactions between diorganodiselenides of type [2‐(R2NCH2)C6H4]2Se2 [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R′2P(S)S]2 (R = Ph, OiPr) resulted in the hypervalent [2‐(R2NCH2)C6H4]SeSP(S)R′2 [R = Et, R′ = Ph ( 1 ), OiPr ( 2 ); R = iPr, R′ = Ph ( 3 ), OiPr ( 4 )] species. All new compounds were characterized by solution multinuclear NMR spectroscopy (1H, 13C, 31P, 77Se) and the solid compounds 1 , 3 , and 4 also by FT‐IR spectroscopy. The crystal and molecular structures of 3 and 4 were determined by single‐crystal X‐ray diffraction. In both compounds the N(1) atom is intramolecularly coordinated to the selenium atom, resulting in T‐shaped coordination arrangements of type (C,N)SeS. The dithio organophosphorus ligands act monodentate in both complexes, which can be described as essentially monomeric species. Weak intermolecular S ··· H contacts could be considered in the crystal of 3 , thus resulting in polymeric zig‐zag chains of R and S isomers, respectively. 相似文献
12.
V. I. Zdanovich V. Yu. Lagunova F. M. Dolgushin A. I. Yanovsky M. G. Ezernitskaya P. V. Petrovskii A. A. Koridze 《Russian Chemical Bulletin》1998,47(9):1789-1796
Ruthenium carbonyl triphenylphosphine complexes Ru2(CO)6−n
(PPh3)
n
{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru2(CO)6{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh3 in refluxing toluene. The complexes were characterized by IR and by1H,13C, and31P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation
of the Ru3(CO)8(PPh3){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh3 ligand at the ruthenium atom of the ruthenacyclopentadiene moiety.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998 相似文献
13.
Evans WJ Walensky JR Furche F Ziller JW DiPasquale AG Rheingold AL 《Inorganic chemistry》2008,47(21):10169-10176
To probe the correlation of unusual (C5Me5)(1-) reactivity with steric crowding in complexes such as (C5Me5)3UMe and (C5Me5)3UCl, slightly less crowded (C5Me5)2(C5Me4H)UX analogues (X = Me, Cl) were synthesized and their reactivity was evaluated. The utility of the cationic precursors [(C5Me5)2UMe](1+), 1, and [(C5Me5)2UCl](1+), 2, in the synthesis of (C5Me5)2(C5Me4H)UMe, 3, and (C5Me5)2(C5Me4H)UCl, 4, was also explored. Since the use of precursor [(C5Me5)2UMe][MeBPh3], 1a, is complicated by the equilibrium between 1a and (C5Me5)2UMe2/BPh3, the reactivity of [(C5Me5)2UMe(OTf)]2, 1b, (OTf = O3SCF3) prepared from (C5Me5)2UMe2 and AgOTf, was also studied. Both 1a and 1b react with KC5Me4H to form 3. Complex 4 readily forms by addition of KC5Me4H to [(C5Me5)2UCl][MeBPh3], generated in situ from (C5Me5)2UMeCl and BPh3. Complex 1b was preferred to 1a for the synthesis of (C5Me5)2(C5H5)UMe, 5, and (C5Me5)2UMe[CH(SiMe3)2], 6, from KC5H5 and LiCH(SiMe3)2, respectively. Complex 6 is the first example of a mixed alkyl uranium metallocene complex. Sterically induced reduction (SIR) reactivity was not observed with 3-6 although the methyl displacements from the (C5Me5)(1-) ring plane for 3 are the closest observed to date to those of SIR-active complexes. The (1)H NMR spectra of 3 and 4 are unusual in that all of the (C5Me4H)(1-) methyl groups are inequivalent. This structural rigidity is consistent with density-functional theory calculations. 相似文献
14.
Reactions of Cyclostibanes, (RSb)n [R = (Me3Si)2CH, n = 3; Me3CCH2, n = 4, 5] with the Transition Metal Carbonyl Complexes [W(CO)5(thf)], [CpxMn(CO)2(thf)], [CpxCr(CO)3]2, and [Co2(CO)8]; Cpx = MeC5H4 (RSb)3 [R = (Me3Si)2CH] reacts with [W(CO)5(thf)], [CpxMn(CO)2(thf)], or [Co2(CO)8] to give [(RSb)3W(CO)5] ( 1 ), [RSb{Mn(CO)2Cpx}2] ( 2 ) or [RSbCo(CO)3]2 ( 3 ). The reaction of (R′Sb)n (n = 4, 5; R′ = Me3CCH2) with [CpxCr(CO)3]2 leads to [(R′Sb)4{Cr(CO)2Cpx}2] ( 4 ); Cpx = MeC5H4, thf = Tetrahydrofuran. 相似文献
15.
M. Ins García‐Seijo Abraha Habtemariam Damin Fernndez‐Anca Simon Parsons M. Esther García‐Fernndez 《无机化学与普通化学杂志》2002,628(5):1075-1084
The complexes [M(PNHP)I]I (PNHP = bis[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 1 ), Pt ( 2 )) and [M(NP3)I]I (NP3 = tris[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 3 ), Pt ( 4 )) were prepared by interaction of the appropriate aminophosphine in CH2Cl2 with aqueous solutions containing [MCl4]2— salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt2(PNHP)3]I4 ( 2a ) and [Pd3(NP3)2I4]I2 ( 3a ) in the presence of coordinating solvents such as the mixture CD3OD/D2O/DMSO‐d6 and CH2Cl2/CH3OH, respectively. Complex 1 consists of distorted square‐planar cations [Pd(PNHP)I]+ and iodide anions able to establish short N‐H···I interactions of 2.850Å. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square‐planar PdII atoms, PdNP2I and trans‐PdP2I2, NP3 acting as tridentate chelating and bridging ligand, respectively. On the basis of 31P {1H} NMR data it has been shown that each distorted square‐planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by 31P {1H} NMR to have the metal atom bound to the three P atoms of NP3 and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring‐opening process, in the formation of [Pt(NP2PO)(SR)] (RS = Acys ( 4a ), GS ( 4b )) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four‐coordination involving the N atom of the aminophosphine. Compounds [Pt2(PNHP)3]Cl4 ( 2a′ , 2a″ ), [PtAu(PNHP)2I]I2 ( 2b ), and [Pt(PNHP)(ONO2)](NO3) ( 2c ) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO3, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP3)I3 ( 5 ), PdAg2(NP3)I4 ( 6 ) and PdAu(NP3)I3 ( 7 ) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring‐opening. 相似文献
16.
Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C6H4C(O)N(H)P(O)X2, X = NH‐C(CH3)3 ( 1 ), NH‐CH2‐CH=CH2 ( 2 ), NH‐CH2C6H5 ( 3 ), N(CH3)(C6H5) ( 4 ), NH‐CH(CH3)(C6H5) ( 5 ) were synthesized and characterized by 1H, 13C, 31P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. 1H and 13C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. 13C NMR spectrum of compound 4 shows that 2J(P,Caliphatic) coupling constant for CH2 group is greater than for CH3 in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C6H4C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C6H4CN+ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra. 相似文献
17.
Monique Biesemans Andrew Duthie Klaus Jurkschat Ingrid Verbruggen Rudolph Willem Bernhard Zobel 《应用有机金属化学》2003,17(5):298-304
The reaction of the 2,2‐bis(organodichlorostannyl)propane [(Me3Si)2CH(Cl2)Sn]2CMe2 (A) with the corresponding organotin oxide {[(Me3Si)2CH(O)Sn]2CMe2}2 (B) does not provide the corresponding normally expected tetraorganodistannoxane {[(Me3Si)2CH(Cl)SnCMe2Sn(Cl)CH(SiMe3)2]O}n but a complex reaction mixture. One major product, namely the 2,4,6,8‐tetraorgano‐2,6‐dichloro‐1,5,9‐trioxa‐2,4,6,8‐tetrastannabicyclo[3.3.1]nonane derivative [(Me3Si)2CHSnCMe2Sn(Cl)CH(SiMe3)2]2O3 (C) was identified in situ by 2D 1H? 119Sn and 1H? 13C heteronuclear multiple quantum coherence and heteronuclear multiple bond correlation NMR spectroscopy as well as electrospray mass spectrometry. Compound C is proposed to be in equilibrium with an ionic species C′, the cation of which has an adamantane‐type structure. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
18.
19.
Novel Silver‐Telluride Clusters Stabilised with Bidentate Phosphine Ligands: Synthesis and Structure of {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞, [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl], and [Ag38Te13(Te t Bu)12(Ph2P(CH2)2PPh2)3] Bidentate phosphine ligands have been found effective to stabilise polynuclear cores containing silver and chalcogenide ligands. They can act as intra and intermolecular bridges between the silver centres. The clusters {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞ ( 1 ), [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl] ( 2 ), and [Ag38Te13(TetBu)12(Ph2P(CH2)2PPh2)3] ( 3 ) have been prepared and their molecular structure determined. Compound 2 and 3 are molecular structures with separated cluster cores while 1 forms a polymeric chain bridged by phosphine ligands. ( 1 : space group P21/c (No. 14), Z = 4, a = 3518,1(7) pm, b = 2260,6(5) pm, c = 3522,1(7) pm, β = 119,19(3)°; 2 : space group R3 (No. 148), Z = 6, a = b = 3059,4(4) pm, c = 5278,8(9) pm; 3: space group Pccn (No. 56), Z = 4, a = 3613,0(9) pm, b = 3608,6(7) pm, c = 2153,5(8) pm) 相似文献
20.
Alpar Pöllnitz Sevil Irisli Cristian Silvestru Anca Silvestru 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):910-919
The new organophosphorus proligand (OPPh2)(O2SMe)NR (R = C6H3Pri 2–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph2P(O)NR] with MeSO2Cl in a 1:1 molar ratio. The precursor Ph2P(O)NHR (1), as well as its thio analogue Ph2P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O?P(C)2–N–S(C)(?O)2 skeleton. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献